Binder resin for polyolefin resin, process for producing the same, and uses thereof

ABSTRACT

The invention provides a binder resin and a primer composition, paint composition, ink composition an adhesive composition with excellent gasohol resistance, adherence, weather resistance, etc. to polyolefinic resins and relates to a binder resin for polyolefinic resins comprising carboxyl group-containing chlorinated polyolefin (II), which contains not more than 2% of a component with molecular weight of 2,000 or lower and which has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), that is the value Mw/Mn of not more than 4.

BACKGROUND OF THE INVENTION

The present invention relates to a binder resin applicable topolyolefinic resins, for example, polypropylene, polyethylene,ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc.In more detail, it relates to a primer, paint, ink and adhesivecomposition to be used for the purpose of protection or beautifulornament of polyolefinic resin moldings, films, etc.

Because of high productivity and broad degree of freedom for design aswell as many advantages of light weight, antirust, shock resistance,etc., in recent years, plastics are used very frequently as thematerials for automotive parts, electrical parts, building materials,food packaging film, etc. Above all, because of low price and manyexcellent properties such as moldability, chemical resistance, heatresistance, water resistance and good electrical characteristics,polyolefinic resins are used in broad range as industrial materials andare one of the materials that the growth of demand is most expected infuture.

Different from synthetic resins with polarity such as polyurethaneresin, polyamide resin, acrylic resin, polyester resin, etc., however,polyolefinic resin is nonpolar and crystalline, leading to drawbacks ofdifficult paintability and adhesion.

For the painting and adhesion onto such hard-adherent polyolefinicresin, low-chlorinated polyolefin that has strong adherence ontopolyolefinic resin has been used so far as a binder resin.

For example, in Japanese Unexamined Patent Publication Nos. Sho 57-36128and Sho 59-166534Japanese Patent Publication No. Sho 63-36624, etc.,low-chlorinated polypropylene or low-chlorinated propylene-α-olefincopolymer with chlorine content of 5 to 50%, containing carboxylic acidand/or carboxylic anhydride, is proposed as a painting primer or coatingbinder resin onto polyolefinic moldings.

Moreover, a composition (Japanese Unexamined Patent Publication Nos. Hei4-248845 and 5-25405) having modified copolymer obtainable by graftcopolymerizing α, β-unsaturated vinyl monomer containing hydroxyl grouponto styrene.conjugated diene block copolymer, followed by furtherchlorination, as an essential component, a composition (JapaneseUnexamined Patent Publication No. Hei 5-25405) having chlorinatedproduct of graft modified product from styrene.isoprene block copolymeras an essential component, a composition (Japanese Unexamined PatentPublication Nos. Hei 5-112750 and Hei 5-112751) having chlorinatedproduct of graft modified product from propylene-ethylene-α-olefinrandom copolymer as an essential component, etc. are also proposed.

Although these compositions exhibit good adherence onto hard-adherentpolyolefin, they are remarkably poor in the “gasohol resistance test”being a criterion of solvent resistance, that is, in a testing methodwherein painted plate is soaked into a gasoline/alcohol mixed solution(gasohol) obtainable by adding 10% of lower alcohol such as methanol orethanol to regular gasoline and whether the solvent resistance is goodor bad is judged by a time until the painted film is peeled off.

Also, a method of crosslinking carboxyl group-containing chlorinatedpolyolefin with epoxy resin that can be seen in Japanese PatentPublication Nos. Sho 63-50381 and Hei 01-16414 and Japanese UnexaminedPatent Publication No. Hei 8-100032, etc., is excellent in the socalledgasoline resistance to soak only in regular gasoline, but poor in thegasohol resistance property.

Further, such descriptions can be seen that a composition (JapaneseUnexamined Patent Publication Nos. Hei 7-247381 and Hei 7-247382) havingmodified chlorinated polyolefin obtained by reacting carboxylgroup-containing chlorinated polyolefin with low-molecular diol orlow-molecular compound containing hydroxyl group and amino group as anessential component and a composition (Japanese Unexamined PatentPublication No. Hei 10-158447) obtained by mixing carboxylgroup-containing chlorinated polyolefin with acrylic-modifiedchlorinated polyolefin that was modified with acrylic resin with glasstransition point of higher than 60° C., etc. are excellent in thegasohol resistance, but it is difficult to say that both really satisfythe gasohol resistance.

The invention provides a primer composition with improved gasoholresistance and adherence usable for painting the moldings, sheets, etc.of polyolefinic resins.

SUMMARY OF THE INVENTION

The primer composition of the invention that solves the subjectaforementioned is a binder resin for polyolefinic resins comprisingcarboxyl group-containing chlorinated polyolefin obtainable by graftcopolymerizing at least one kind of unsaturated carboxylic monomerselected from carboxylic acid and/or carboxylic anhydride ontopolyolefin (I) in amounts of 1 to 10 wt. % and then chlorinating tochlorine content of 10 to 30 wt. %, and having carboxyl group-containingchlorinated polyolefin (II), which contains only not more than 2% of acomponent with molecular weight of 2,000 or lower, being thelow-molecular weight region of said carboxyl group-containingchlorinated polyolefin, and which has a value of Mw/Mn, being a ratio ofweight average molecular weight (Mw) to number average molecular weight(Mn), of not more than 4, as a major binder resin.

DETAILED DESCRIPTION OF THE INVENTION

The polyolefin graft copolymerized with unsaturated carboxylic acidconcerning the invention can be obtained by melting polyolefin underheat and, if need be, reducing viscosity or degrading it by thermaldecomposition, and then by graft copolymerizing unsaturated carboxylicacid monomer of carboxylic acid and/or carboxylic anhydride in amountsof 1 to 10 wt. % batchwise or continuously in the presence of radicalgenerator.

As the polyolefins (I), crystalline polypropylene, noncrystallinepolypropylene, propylene-α-olefin copolymer etc. can be used solely orby mixing two or more kinds, but, from the points of workability andadhesiveness of binder resin, a crystalline polypropylene with weightaverage molecular weight of 10,000 to 150,000, a propylene-α-olefincopolymer with weight average molecular weight of 10,000 to 150,000 inwhich 70 to 97 mol % of propylene component is contained and number ofcarbon atoms is 2 or 4 to 6, a propylene-butene-ethylene terpolymer withweight average molecular weight of 10,000 to 150,000 in which 70 to 97mol % of propylene component, 2 to 25 mol % of butene component and 2 to25 mol % of ethylene component are contained, or the like can be used.In the case of propylene-α-olefin copolymer, the α-olefin unit ispreferable to be at least one kind of α-olefin with number of carbonatoms of 2 or 4 to 6 selected from, for example, ethylene, 1-butene,1-pentene, 4-methyl-1-pentene, 3-methyl-l-pentene and 1-hexene.

If the weight average molecular weight of raw material polyolefin (I) isunder 10,000 or the propylene component is under 70 mol %, then theadherence to polyolefinic resin and the gasohol resistance become poor,and, if the weight average molecular weight exceeds 150,000, then theprimer does not become fine particles when painting by air spray etc. tospoil the beautiful appearance of painted surface, which isunpreferable. Moreover, if the number of carbon atoms of α-olefin ofpropylene-α-olefin copolymer exceeds 6, then the adherence topolypropylene resin becomes poor. Furthermore, the propylene content ofpropylene-butene-ethylene copolymer being terpolymer is preferable to be70 to 97 mol % as described above, the butene content is preferable tobe 2 to 25 mol % and the ethylene content is preferable to be 2 to 25mol %.

The unsaturated carboxylic acid monomers usable for introducing carboxylgroup include acrylic acid, methacrylic acid, maleic acid, maleicanhydride, fumaric acid, intaconic acid, itaconic anhydride, aconiticacid, aconitic anhydride, etc. and the amount of graft copolymerizationis preferable to be 1 to 10 wt. % to polyolefin. If under 1%, thegasohol resistance becomes poor and the adherence to upper paint alsobecomes poor. If over 10%, the adherence to polyolefinic resin becomespoor and simultaneously increased solution viscosity due to hydrogenbond is seen, resulting in gelation on preservation and poor workabilityby air spray etc.

The radical generators to be used for the graft copolymerizationreaction between polyolefin (I) and unsaturated carboxylic acid monomerinclude, for example, peroxides such as di-tert-butyl peroxide,tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxide benzoate, methyl ethyl ketone peroxide and di-tert-butyldiperphthalate and azonitriles such as azobisisobutyronitrile.

The chlorine content of carboxyl group-containing chlorinated polyolefin(II) to be used in the invention is preferable to be 10 to 30 wt. %. Ifthe chlorine content is under 10 wt. %, then the solubility into organicsolvents such as toluene and xylene is poor and uniform solution cannotbe obtained, resulting in gelation at low temperature or generation ofgrains, hence the solution becomes not to be applied as a primer. If thechlorine content exceeds 30 wt. %, the adherence to polyolefinic resinand the gasohol resistance become poor, which is unpreferable.

The less the component of low-molecular weight region of carboxylgroup-containing chlorinated polyolefin (II) to be used in theinvention, the better the gasohol resistance. That is, if the componentwith molecular weight of 2,000 or lower is contained over 2%, thegasohol resistance becomes poor remarkably. Moreover, the ratio ofweight average molecular weight (Mw) to number average molecular weight(Mn) of (II), that is, the value of Mw/Mn is preferable to be not morethan 4. When it exceeds 4 due to increase in the component ofhigh-molecular weight region, the primer does not become fine particleswhen painting by air spray etc. and the beautiful appearance of coatedsurface is spoiled, which is unpreferable. When it exceeds 4 due toincrease in the component of low-molecular weight region, the gasoholresistance becomes poor.

Besides, the content of low-molecular weight component with molecularweight of 2,000 or lower and the ratio of weight average molecularweight (Mw) to number average molecular weight (Mn), that is, Mw/Mn weredetermined by means of gel permeation chromatograph (GPC), usingpolystyrene with known molecular weight and narrow molecular weightdistribution as a standard substance.

The carboxyl group-containing chlorinated polyolefin (II) to be used inthe invention can be obtained by warming to completely dissolvepolyolefin that was graft copolymerized with unsaturated carboxylic acidinto solvents for chlorinating reaction, for example, chloroform, carbontetrachloride, tetrachloroethylene, tetrachloroethane, etc., and thenblowing-in chlorine gas to react at applied pressure or ambient pressurein the presence of radical generator as described above or underirradiation of ultraviolet rays, or in the absence of these radicalgenerator and ultraviolet rays. The chlorinating reaction is conductedunusually at a temperature between 60° C. and 120° C.

As the method for removing low-molecular weight component of carboxylgroup-containing chlorinated polyolefin, two methods of (1) a method forextracting to remove low-molecular weight component in carboxylgroup-containing polyolefin before chlorination with solvent and (2) amethod for extracting to remove low-molecular weight component incarboxyl group-containing chlorinated polyolefin after chlorination withsolvent can be proposed.

For removing low-molecular weight component by the method (1), it ispossible to remove by making carboxyl group-containing polyolefin beforechlorination powdery, granular, pellet-like or molten state and byadding sole solvent selected from a group consisting of aliphatichydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenatedhydrocarbon, alcohols, esters, ketones and ethers with boiling point oflower than 120° C. or a mixed solvent thereof to dissolve out thelow-molecular weight component into these solvents within a temperaturerange of 10 to 100° C.

The reason why the boiling point of solvent was made to be lower than120° C. is because of that, if the boiling point is too high, solventbecomes to be liable to remain in the carboxyl group-containingpolyolefin or carboxyl group-containing chlorinated polyolefin (II),resulting in chlorination of said solvent or decreased physicalproperties of primer, which is unpreferable.

The reason why the temperature on extraction was made 10 to 100° C. isbecause of that, if under 10° C., removal of low-molecular weightcomponent by extraction becomes incomplete, which is unpreferable. Also,if over 100° C., even high-molecular weight component is removed todecrease the recovery rate, which is unpreferable. When using a solventwith boiling point of under 100° C., it is preferable to conduct thesolvent extraction in a completely closed-up pressure vessel.

The method for removing low-molecular weight component by the method (2)is also possible to conduct with carboxyl group-containing chlorinatedpolyolefin, following the method (1). When the carboxyl group-containingchlorinated polyolefin is in solution, the temperature on extraction ispreferable to be as low as possible, but, if under 0° C., the solventextraction of low-molecular weight component cannot be conductedefficiently, because of too high viscosity. If the temperature becomeshigher than room temperature, then the carboxyl group-containingchlorinated polyolefin dissolves into extracting solvent in largequantity to decrease the recovery rate, which is unpreferable. When thecarboxyl group-containing chlorinated polyolefin is solid article, thehigher the extraction temperature, the better, but, if over 100° C.,dehydrochloric acid etc. are caused to bring to instability, which isunpreferable.

As typical solvents with boiling point of under 120° C. for removinglow-molecular weight component, in the case of aliphatic hydrocarbon,pentane, 2-methylpentane, hexane, 2,2-dimethylbutane,2,3-dimethyl-butane, heptane, 2-methylhexane, 3-methylhexane,2,4-dimethylpentane, petroleum ether, petroleum benzine, etc. can beexemplified. In the case of aromatic hydrocarbon, benzene, toluene, etc.can be exemplified. In the case of alicyclic hydrocarbon, cyclopentane,methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane,etc. can be exemplified. In the case of halogenated hydrocarbon,trichloromethane, tetrachloromethane, 1,1-dichloroethane,1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane,1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, etc. canbe exemplified. In the case of alcohols, methanol, ethanol, 2-propanol,1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol,3-pentanol, etc. can be exemplified. In the case of esters, propylformate, butyl formate, methyl acetate, ethyl acetate, propyl acetate,isopropyl acetate, isobutyl acetate, secbutyl acetate, etc. can beexemplified. In the case of ketones, acetone, methyl ethyl ketone,2-pentanone, 3-pentanone, methyl isobutyl ketone, etc. can beexemplified. In the case of ethers, diethyl ether, dipropyl ether,diisopropyl ether, etc. can be exemplified.

The carboxyl group-containing chlorinated polyolefin (II) to be used inthe invention can be used as it is by coating or spray painting in thestate of clear varnish. But, it can also be used as a primer, paint andink for polyolefinic resin moldings and films by adding titaniumdioxide, carbon black, aluminum paste, coloring pigment, etc. and, ifneed be, other additives, for example, ultraviolet absorber,antioxidant, pigment sedimentation preventer, etc. followed by kneading.Moreover, it can also be used as an adhesive for those substrates.

Moreover, the carboxyl group-containing chlorinated polyolefin (II)exhibits balanced physical properties of painted film by itself, but, byadding alkyd resin, acrylic resin, polyacrylic polyol, polyester resin,polyesterpolyol, polyether resin, polyetherpolyol or polyurethane resinfor use, more characteristic binder resin composition can be obtained.

The addition of said resins is very useful, since the adherence ontoupper coating paint and the weather resistance that was a drawback ofchlorinated polyolefinic resin improve. From such reason, by allowing tohave a resin mixed at a ratio by weight of carboxyl group-containingchlorinated polyolefin (II)/said resin group=3/7 to 9/1 as a majorbinder resin, more improved binder resin composition can be obtained.

Namely, contrary to the facts that, when said resin group is mixed withconventional carboxyl group-containing chlorinated polyolefin, not onlythe adherence onto polyolefin decreases, but also the gasohol resistancedecreases remarkably, in the case of the carboxyl group-containingchlorinated polyolefin (II) of the invention, mixing of said resin groupeven up to 70% at maximum does not injure the adherence and the gasoholresistance. Furthermore, when titanium dioxide, carbon black, coloringpigment, etc. are kneaded beforehand with said resin and then (II) ismixed, there is an advantage that stabilized pigment dispersion can beachieved. That is, minimum requirement level of said resin to achievestabilized pigment dispersion is 10%.

For the chlorinated resin like the carboxyl group-containing chlorinatedpolyolefin.(II) obtainable by the method aforementioned, epoxy compoundhas been added so far as a stabilizer for use. Although the epoxycompound is not particularly restricted, one compatible with chlorinatedresin is preferable, and such epoxy compound with epoxy equivalent ofaround 100 to 500 and with one or more epoxy group per molecule can beexemplified.

For example, epoxidated soybean oil and epoxidated linseed oilobtainable by epoxidating vegetable oils having natural unsaturatedgroup with peracids such as peracetic acid, epoxidated fatty acid estersobtainable by epoxidating unsaturated fatty acids such as oleic acid,tall oil fatty acid and soybean oil fatty acid, epoxidated alicycliccompounds represented by epoxidated tetrahydrophthalate, and productsobtainable by condensing bisphenol A or polyhydric alcohol withepichlorohydrin, for example, bisphenol A glycidyl ether, ethyleneglycol glycidyl ether, propylene glycol glycidyl ether, glycerolpolyglycidyl ether, sorbitol polyglycidyl ether, etc. are exemplified.Moreover, monoepoxy compounds represented by butyl glycidyl ether,2-ethyl-hexyl glycidyl ether, decyl glycidyl ether, stearyl glycidylether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenylglycidyl ether, tert-butylphenyl glycidyl ether, phenol polyethyleneoxide glycidyl ether, etc. are exemplified. Moreover, metallic soapssuch as calcium stearate and lead stearate, organometallic compoundssuch as dibutyl tin dilaurate and dibutyl tin maleate and hydrotalcitecompounds, which are used as the stabilizers of poly (vinyl chloride)resin, can also be used, and it doesn't matter whether these are used incombination.

The carboxyl group-containing chlorinated polyolefin (II) obtainable bythe method aforementioned can be used by replacing the solvent toaromatic hydrocarbon such as toluene or xylene, or alicyclic hydrocarbonsuch as cyclohexane or methylcyclohexane, being good solvents, aftercompletion of chlorinating reaction and after distillation ofchlorination solvent, and then by adding stabilizer such as epoxycompound. In the case of the carboxyl group-containing chlorinatedpolyolefin (II) of the invention, however, due to the hydrogen bondoriginating from carboxyl group contained, the solution viscosityincreases over time. For preventing this, it is possible to partiallyadd a solvent with polarity, for example, ester type solvent such asethyl acetate, ketone type solvent such as methyl ethyl ketone, ethertype solvent such as tetrahydrofuran, or alcohol type solvent such asisopropanol for use. Above all, the effect of alcohol type solvent isconspicuous and it is only necessary to add 1 to 10 wt. % to the solventcomposition.

Moreover, it may also be safe that, after completion of chlorinatingreaction and after removal of hydrochloric acid in the solvent forchlorinating reaction such as chloroform, epoxy compound or the like isadded as a stabilizer and the stabilized material is solidified bysupplying to a vent extruder equipped with solvent-removing suction atthe part of screw shaft, and, thereafter, it is dissolved into solventsuch as toluene. The solidification can be implemented by the publiclyknown method, for example, by using a vent extruder equipped withunderwater cutting pelletizer at the outlet part of extruder, apelletizer capable of cutting strand-like resin, and the like.

The feature of the invention lies in the carboxyl group-containingchlorinated polyolefin (II) with low-molecular weight component ofcarboxyl group-containing chlorinated polyolefin removed and withmoderate ratio of weight average molecular weight (Mw) to number averagemolecular weight (Mn), that is, Mw/Mn value, thus providing a primercomposition that exhibits excellent adherence and gasohol resistance topolyolefinic resins. Although it is not clear why the removal oflow-molecular weight component improves the gasohol resistance, it isconsidered that these low-molecular weight components are additionproducts of chlorine and carboxylic acid to olefin oligomers producedthrough the decomposition of polyolefin by heat and catalyst. Ifconsidering that the swelling or dissolution of this component intogasoline and alcohol being components of gasohol lowers the gasoholresistance, it can be said that the removal of low-molecular weightcomponent is one of the reasons that improves the gasohol resistance.

In following, the invention will be illustrated concretely based onexamples, but the invention is not confined to these.

EXAMPLE Preparing Example 1

In a three-neck flask attached with stirrer, dropping funnel and coolingpipe for refluxing monomer, 5 kg of crystalline polypropylene withweight average molecular weight of 40,000 were placed and moltencompletely in an oil bath kept constantly at 180° C. The inside of flaskwas replaced with nitrogen, 300 g of maleic anhydride were put in overabout 5 minutes while stirring, and then 20 g of di-tert-butyl peroxidedissolved into 50 ml of heptane were put in over about 30 minutes fromdropping funnel. At this time, the inside of system was kept at 180° C.After continued the reaction further for 15 minutes, unreacted maleicanhydride was removed over about 30 minutes while reducing the pressurein flask by aspirator to obtain maleic anhydride-modified polypropylenecopolymerized with maleic anhydride.

Next, after cooling to ambient temperature, this product was pulverizedand 5 kg thereof were thrown into a pressure vessel attached withstirrer. Then, 5 kg of n-hexane (bp. 68.7° C.) and 5 kg of methyl ethylketone (bp. 79.6° C.) were put in to dissolve out low-molecular weightcomponent into solvent while stirring for 4 hours at 100° C. Followingthis, solvent was taken off by filtration, the filter residue was washedwith said solvent and then it was dried for 24 hours at 70° C. in ablast dryer to obtain 4.65 kg of maleic anhydride-modified polypropylenewith low-molecular weight component removed.

Next, 4 kg of maleic anhydride-modified polypropylene with low-molecularweight component removed were thrown into a glass-lined reactor, 80liters of chloroform were added, and, after sufficiently dissolved at120° C. under pressure of 4 kg/cm², chlorine gas was blown-in from thebottom of reactor. while keeping the temperature at 110° C. to conductthe chlorination reaction until the chlorine content became 25 wt. %.The solvent chloroform was distilled off by evaporator to replace itwith a mixed solvent of toluene/cyclohexane=65/35 (wt.), and Epicote 828(condensation product of bisphenol A with epichloro-hydrin, an epoxyresin with epoxy equivalent of 184 to 194, from Shell Chemicals Corp.)was added in amounts of 4% based on solids as a stabilizer, followed byconcentration adjustment, thus obtaining carboxyl group-containingchlorinated polypropylene (A-1) in the form of solution with solidsconcentration of 20%.

When measuring the molecular weight of (A-1), Mw/Mn=2.90 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 0.25%.

Preparing Example 2

In a three-neck flask attached with stirrer, dropping funnel and coolingpipe for refluxing monomer, 5 kg of propylene-butene-ethylene copolymer(terpolymer) with weight average molecular weight of 120,000 consistingof 75 mol % of propylene component, 17 mol % of butene component and 8mol % of ethylene component were placed and molten completely in an oilbath kept constantly at 180° C. The inside of flask was replaced withnitrogen, 350 g of maleic anhydride were thrown-in over about 5 minuteswhile stirring, and then 35 g of dicumyl peroxide dissolved into 50 mlof heptane were put in over about 30 minutes from dropping funnel. Atthis time, the inside of system was kept at 180° C. After continued thereaction further for 15 minutes, unreacted maleic anhydride was removedover about 30 minutes while reducing the pressure in flask by aspiratorto obtain maleic anhydride-modified propylene-butene-ethylene copolymercopolymerized with maleic anhydride.

Next, this product was made pellet-like and 5 kg thereof were put into athree-neck flask attached with stirrer and cooling pipe for refluxingsolvent. Then, 10 kg of ethyl acetate (bp. 77.1° C.) were thrown-in todissolve out low-molecular weight component into solvent while refluxingsolvent for 4 hours at 77° C. Following this, solvent was taken off byfiltration, the filter residue was washed with said solvent and then itwas dried for 24 hours at 70° C. in a blast dryer to obtain 4.75 kg ofmaleic anhydride-modified propylene-butene-ethylene copolymer withlow-molecular weight component removed.

Next, 4 kg of product with low-molecular weight component removed wereput into a glass-lined reactor, 80 liters of chloroform were added, and,after sufficiently dissolved at 100° C. by stirring under pressure of 3kg/cm², chlorine gas was blown-in from the bottom of reactor whileirradiating ultraviolet rays and keeping the reaction temperature at 80°C. to conduct the chlorination reaction until the chlorine contentbecame 12 wt. %. The solvent chloroform was distilled off by evaporatorto replace it with toluene, and Epicote 828 was added in amounts of 4%based on solids as a stabilizer, followed by concentration adjustment,thus obtaining carboxyl group-containing chlorinatedpropylene-butene-ethylene copolymer (A-2) in the form of toluenesolution with solids concentration of 20%.

When measuring the molecular weight of (A-2), Mw/Mn=3.85 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 1.20%.

Preparing Example 3

Except that propylene-ethylene copolymer with weight average molecularweight of 50,000 consisting of 94 mol % of propylene component and 6 mol% of ethylene component was sampled, maleic anhydride was copolymerizedby the method quite similar to preparing example 2 to obtain maleicanhydride-modified propylene-ethylene copolymer.

Next, after cooling to ambient temperature, this product was pulverizedand 5 kg thereof were put into a three-neck flask attached with stirrerand cooling pipe for refluxing solvent. Then, 10 kg of methyl ethylketone (bp. 79.6° C.) were put in to dissolve out low-molecular weightcomponent into solvent while refluxing for 4 hours at 79° C. Followingthis, solvent was taken off by filtration, the filter residue was washedwith said solvent and then it was dried for 24 hours at 70° C. in ablast dryer to obtain 4.7 kg of maleic anhydride-modifiedpropylene-ethylene copolymer with low-molecular weight componentremoved.

Next, 4 kg of this product were thrown into a glass-lined reactor withstirrer, 80 liters of chloroform were added, and, after sufficientlydissolved at. 110° C. under pressure of 3 kg/cm², 5 g ofazobisisobutyronitrile were added as a reaction catalyst and chlorinegas was blown-in from the bottom of reactor to conduct the chlorinationreaction until the chlorine content became 17 wt. %. After the solventchloroform was distilled off partially by evaporator, tert-butylphenylglycidyl ether (monoepoxy) was added in amounts of 5% based on solids asa stabilizer, and residual chloroform was removed completely with a ventextruder installed with vent port for distilling it under reducedpressure to obtain carboxyl group-containing chlorinatedpropylene-ethylene copolymer in the form of solid product. Then, thissolid product was dissolved into toluene to obtain (A-3) that wasadjusted to toluene solution with solids concentration of 20%.

When measuring the molecular weight of (A-3), Mw/Mn=3.65 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 0.75%.

Preparing Example 4

Five kg of maleic anhydride-modified polypropylene, in which thelow-molecular weight component was not removed in Preparing example 1were put into a glass-lined reactor and 80 liters of chloroform wereadded. After sufficiently dissolved at 120° C. under pressure of 4kg/cm², chlorine gas was blown-in from the bottom of reactor whilekeeping the temperature at 110° C. and irradiating ultraviolet rays toconduct chlorination reaction until the chlorine content became 25 wt.%, and the solvent chloroform (bp. 61.2° C.) was concentrated byevaporator until the solids content became 25%. Then, 1 kg of thisconcentrated liquid was added dropwise into 10 liters of acetone (bp.56.1° C.) at room temperature to cause bread-crumbs-like precipitatesand these precipitates were recovered (recovery rate: 70%) bycentrifugal separation. Besides, the low-molecular weight component isremoved by dissolving out into supernatant.

Next, these precipitates were dried under reduced pressure and, afterEpicote 828 was added in amounts of 4% based on solids as a stabilizer,they were dissolved into a mixed solvent of toluene/cyclohexane=65/35 toobtain carboxyl group-containing chlorinated polypropylene (A-4) withlow-molecular weight component removed in the form of solution withsolids concentration of 20%.

When measuring the molecular weight of (A-4), Mw/Mn=2.55 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 0.12%.

Preparing Example 5

Five kg of maleic anhydride-modified propylene-butene-ethylene copolymerin which the low-molecular weight component was not removed in Preparingexample 2 were thrown into a glass-lined reactor with stirrer and 80liters of chloroform were added. After sufficiently dissolved at 100° C.by stirring under pressure of 3 kg/cm², 5 g of azobisisobutyronitrilewere added as a radical generator and, while keeping this temperature,chlorine gas was blown-in from the bottom of reactor to conductchlorination reaction until the chlorine content became 12 wt. %. Thesolvent chloroform was distilled off by evaporator and replaced withtoluene (b.p. 110.6° C.) to adjust to toluene solution with solidsconcentration of 20%. Then, 1 kg of this solution was added dropwiseinto 10 liters of methanol (bp. 64.5° C.) at temperature of 10° C. tocause bread-crumbs-like precipitates and these precipitates wererecovered (recovery rate: 60%) by centrifugal separation. Besides, thelow-molecular weight component is removed by dissolving out intosupernatant.

Next, these precipitates were dried under reduced pressure and, afterEpicote 828 was added in amounts of 4% based on solids as a stabilizer,they were dissolved into toluene to obtain carboxyl group-containingchlorinated propylene-butene-ethylene copolymer (A-5) in the form totoluene solution with solids concentration of 20%.

When measuring the molecular weight of (A-5), Mw/Mn=3.26 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 0.80%.

Preparing Example 6

Five kg of maleic anhydride-modified propylene-ethylene copolymer inwhich the low-molecular weight component was not removed in Preparingexample 3 were thrown into a glass-lined reactor with stirrer and 80liters of chloroform were added. After sufficiently dissolved at 110° C.under pressure of 3 kg/cm², 5 g of azobisisobutyronitrile were added asa radical generator and, while keeping this temperature, chlorine gaswas blown-in from the bottom of reactor to conduct chlorination reactionuntil the chlorine content became 17 wt. %. After the solvent chloroformwas distilled off by evaporator, tert-butylphenyl glycidyl ether(monoepoxy) was added in amounts of 5% based on solids as a stabilizer,and residual chloroform was removed completely with a vent extruderinstalled with vent port for distilling it under reduced pressure toobtain carboxyl group-containing chlorinated propylene-ethylenecopolymer in the form of pellet-like solid product.

Next, 4 kg of this pellet were put into a three-neck flask attached withstirrer and cooling pipe for refluxing solvent, then 9 kg of ethanol(b.p. 78.3° C.) and 1 kg of cyclohexane (b.p. 80.7° C.) were put in,and, while refluxing the solvent for 4 hours at 78° C., thelow-molecular weight component was dissolved out into solvent. Next,solvent was taken off by filtration and the filter residue was washedwith said solvent, followed by drying under reduced pressure. Therecovery rate at this time was 65%. Then, after tert-butylphenylglycidyl ether was added in amounts of 4% based on solids as astabilizer, the filter residue was dissolved into toluene to obtainmaleic anhydride-modified propylene-ethylene copolymer (A-6) withlow-molecular weight component removed in the form of toluene solutionwith solids concentration of 20%.

When measuring the molecular weight of (A-6), Mw/Mn=2.78 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 0.35%.

Preparing Example 7

Five kg of maleic anhydride-modified polypropylene, in which thelow-molecular weight component was not removed in Preparing example 1were put into a glass-lined reactor and 80 liters of chloroform wereadded. After sufficiently dissolved at 120° C. under pressure of 4kg/cm², chlorine gas was blown-in from the bottom of rector whilekeeping the temperature at 110° C. and irradiating ultraviolet rays toconduct chlorination reaction until the chlorine content became 25 wt.%, and the solvent chloroform was distilled off by evaporator. Aftersolvent was replaced with a mixed solvent of toluene/cyclohexane=65/35(wt.), Epicote 828 was added in amounts of 4% based on solids as astabilizer and concentration was adjusted to obtain carboxylgroup-containing chlorinated polypropylene (B-1) in the form of solutionwith solids concentration of 20%.

When measuring the molecular weight of (B-1), Mw/Mn=5.77 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 3.65%.

Preparing Example 8

Five kg of maleic anhydride-modified propylene-butene-ethylene copolymerin which the low-molecular weight component was not removed in Preparingexample 2 were thrown into a glass-lined reactor with stirrer and 80liters of chloroform were added. After sufficiently dissolved at 100° C.by stirring under pressure of 3 kg/cm², 5 g of azobisisobutyronitrilewere added as a radical generator and, while keeping this temperature,chlorine gas was blown-in from the bottom of reactor to conductchlorination reaction until the chlorine content became 12 wt. %. Afterthe solvent chloroform was distilled off by evaporator and replaced withtoluene, Epicote 828 was added in amounts of 4% based on solids as astabilizer and concentration was adjusted to obtain carboxylgroup-containing chlorinated propylene-butene-ethylene copolymer (B-2)in the form of toluene solution with solids concentration of 20%.

When measuring the molecular weight of (B-2), Mw/Mn=9.58 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 7.05%.

Preparing Example 9

Five kg of maleic anhydride-modified propylene-ethylene copolymer inwhich the low-molecular weight component was not removed in Preparingexample 3 were thrown into a glass-lined reactor with stirrer and 80liters of chloroform were added. After sufficiently dissolved at 110° C.under pressure of 3 kg/cm², 5 g of azobisisobutyronitrile were added asa radical generator and, while keeping this temperature, chlorine gaswas blown-in from the bottom of reactor to conduct chlorination reactionuntil the chlorine content became 17 wt. %. After the solvent chloroformwas distilled off partially by evaporator, tert-butylphenyl glycidylether was added in amounts of 4% based on solids as a stabilizer, andresidual chloroform was removed completely with a vent extruderinstalled with vent port for distilling it under reduced pressure toobtain carboxyl group-containing chlorinated propylene-ethylenecopolymer in the form of solid product. Then, this solid product wasdissolved into toluene to obtain (B-3) that was adjusted to toluenesolution with solids concentration of 20%.

When measuring the molecular weight of (B-3), Mw/Mn=7.06 was observedand the content of low-molecular weight component with molecular weightof less than 2,000 was 4.65%.

The substance of carboxyl group-containing chlorinated polyolefins (II)is shown in Table 1. Moreover, the substance of synthetic resins to beused by mixing with (II) is shown in Table 2.

TABLE 1 Substance of carboxyl group-containing chlorinated polyolefins(II) obtained in preparing examples 1 through 9 Content of molecularChlorine weight less Preparing Raw material content than 2000 examplepolyolefin (%) Mw/Mn (%) 1 (A-1) Crystalline 25 2.90 0.25 polypropylene2 (A-2) Propylene-butene- 12 3.85 1.20 ethylene copolymer 3 (A-3)Propylene-ethylene 17 3.65 0.75 copolymer 4 (A-4) Crystalline 25 2.550.12 polypropylene 5 (A-5) Propylene-butene- 12 3.26 0.80 ethylenecopolymer 6 (A-6) Propylene-ethylene 17 2.78 0.35 copolymer 7 (B-1)Crystalline 25 5.77 3.65 polypropylene 8 (B-2) Propylene-butene- 12 9.587.05 ethylene copolymer 9 (B-3) Propylene-ethylene 17 7.06 4.65copolymer

Solids concentrations in preparing examples 1 through 9 are all 20%.

Examples 1 Through 12 and Comparative Examples 1 Through 3

Sampling was made according to the formulation recipes shown in Table 2and, after kneading for 1 hour in a sand grinder mill, viscosity wasadjusted with xylene so as to give 13 to 14 seconds/20° C. through Fordcup No. 4 to make each primer. Besides, synthetic resins to be used bymixing with carboxyl group-containing chlorinated polyolefin (II) areshown in Table 3.

Next, this primer was spray coated onto a polypropylene plate that waswashed with water so as the film thickness to become 10 μm. Severalminutes later, cure type two-component urethane paint was spray coatedso as the film thickness to become 30 to 40 μm and, after dried forabout 15 minutes at room temperature, this was dried forcedly for 30minutes at 80° C. After allowed to stand for 3 days, tests of paintedfilm were performed. The test results of painted film are shown in Table4.

TABLE 2 Formulation recipe of primer [parts by weight] Resin Ex. Ex. Ex.Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Com. Com. Com. composition 1 2 3 4 56 7 8 9 10 11 12 ex. 1 ex. 2 ex. 3 A-1 100 — — — — — 30 — — — — — — — —A-2 — 100 — — — — — 60 — — — — — — — A-3 — — 100 — — — — — 50 — — — — —— A-4 — — — 100 — — — — — 70 — — — — — A-5 — — — — 100 — — — — — 80 — —— — A-6 — — — — — 100 — — — — — 90 — — — B-1 — — — — — — — — — — — — 100— — B-2 — — — — — — — — — — — — — 100 — B-3 — — — — — — — — — — — — — —100 Desmophene — — — — — — 23.3 — — — — — — — — A160 Pararoid — — — — —— — 8 — — — — — — — A-11 Phthalkyd — — — — — — — — 20 — — — — — — V904Nippolan — — — — — — — — — 6- — — — — — 165 Desmophene — — — — — — — — —— 4 — — — — 1900U Nippolan — — — — — — — — — — — 6.7 — — — 5138 Titanium13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.213.2 dioxide Carbon 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 black Xylene — — — — — — 46.7 32 30 24 16 3.3 — — —(Abbreviation) Ex.: Example, Com. ex.: Comparative example

TABLE 3 Substance of synthetic resins to be used by mixing with carboxylgroup-containing chlorinated polyolefins (II) obtained in Preparingexamples Heating Content residue of OH Type of resin (%) (%) SupplierDesmophene Acrylic polyol  60 1.6 Bayer A160 Pararoid Acrylic resin 100— Rohm & Haas A-11 Phthalkyd Alkyd resin  50 — Hitachi Chemical Co. V904Nippolan Polyesterpolyol 100 1.7 Nippon Polyurethane 165 Industry Co.Demophene Polyetherpolyol 100 1.7 Bayer 1900U Nippolan Urethane resin 30 — Nippon Polyurethane 5138 Industry Co.

TABLE 4 Test results of painted film (Performance test of primer) Ad-her- Warm water Moisture Gasohol resistance ence resistance resistanceExam- After soaking for 100/ No abnormalities No abnormalities ple 5 hr,no peeling- 100 of painted of painted 1 off of painted surface, Goodsurface, Good film adherence adherence Exam- After soaking for 100/ Noabnormalities No abnormalities ple 3 hr, peeling off 100 of painted ofpainted 2 of painted film surface, Good surface, Good adherenceadherence Exam- After soaking for 100/ No abnormalities No abnormailtiesple 4 hr, peeling-off 100 of painted of painted 3 of painted filmsurface, Good surface, Good adherence adherence Exam- After soaking for100/ No abnormalities No abnormalities ple 5 hr, no peeling- 100 ofpainted of painted 4 off of painted surface, Good surface, Good filmadherence adherence Exam- After soaking for 100/ No abnormalities Noabnormalities ple 4 hr, peeling-off 100 of painted of painted 5 ofpainted film surface, Good surface, Good adherence adherence Exam- Aftersoaking for 100/ No abnormalities No abnormalities ple 5 hr, peeling-off100 of painted of painted 6 of painted film surface, Good surface, Goodadherence adherence Exam- After soaking for 100/ No abnormalities Noabnormalities ple 2 hr, peeling- 100 of painted of painted 7 off ofpainted surface, Good surface, Good film adherence adherence Exam- Aftersoaking for 100/ No abnormalities No abnormalities ple 2 hr, peeling-off100 of painted of painted 8 of painted film surface, Good surface, Goodadherence adherence Exam- After soaking for 100/ No abnormalities Noabnormalities ple 2 hr, peeling-off 100 of painted of painted 9 ofpainted film surface, Good surface, Good adherence adherence Exam- Aftersoaking for 100/ No abnormalities No abnormalities ple 3 hr, peeling-off100 of painted of painted 10 of painted film surface, Good surface, Goodadherence adherence Exam- After soaking for 100/ No abnormalities Noabnormalities ple 2 hr, peeling-off 100 of painted of painted 11 ofpainted film surface, Good surface, Good adherence adherence Exam- Aftersoaking for 100/ No abnormalities No abnormalities ple 4 hr, peeling-off100 of painted of painted 12 of painted film surface, Good surface, Goodadherence adherence Com. After soaking for 100/ No abnormalities Noabnormalities exam- 50 min, peeling- 100 of painted of painted ple 1 offof painted surface, Good surface, Good film adherence adherence Com.After soaking for 100/ No abnormalities No abnormalities exam- 30 min,peeling- 100 of painted of painted ple 2 off of painted surface, poorsurface, poor film adherence adherence Com. After soaking for 100/ Noabnormalities No abnormalities exam- 40 min, peeling- 100 of painted ofpainted ple 3 off of painted surface, Good surface, poor film adherenceadherence

Testing Methods of Painted Film 1 (Performance Test of Primer)

Gasohol Resistance

A painted plate cut at both ends was soaked into a mixed gasoline ofregular gasoline: ethanol=9:1, and judgment was made by the time until adistance of about 2 mm was peeled off from the end of cut paintedsurface.

Adherence

A hundred cross-cuts reaching the base were made on the painted surfaceat intervals of 1 mm and cellophane adhesive tape was adhered closely.Then, it was peeled off in the direction of 180° to examine the numberof remaining cross-cuts.

Warm Water Resistance

A painted plate was soaked for 240 hours into warm water of 40° C. toexamine the state of painted film. Moreover, a scratch (x mark) reachingthe base was carved on the painted surface and cellophane adhesive tapewas adhered closely thereon. Then, it was peeled off in the direction of180° to examine the adherence of painted film.

Moisture Resistance

A specimen was allowed to stand for 240 hours in an atmosphere of 50° C.and relative humidity of 98%, and the state and adherence of paintedfilm were examined by the method similar to that for warm waterresistance.

Examples 13 Through 18 and Comparative Examples 4 Through 6

Sampling was made according to the formulation recipes of painted shownin Table 5 and, after kneading for 1 hour in a sand grinder mill,viscosity was adjusted with xylene so as to give 12 to 13 seconds/20° C.through Ford cup No. 4 to make white paint.

Next, this white paint was spray coated onto a polypropylene plate thatwas washed with water so as the film thickness to become 40 μm and,after dried for 15 minutes at room temperature, this was dried forcedlyfor 30 minutes at 80° C. After allowed to stand for a week in the room,tests of painted film were performed. The test results of painted filmare shown in Table 6.

TABLE 5 Formulation recipe of paint [parts by weight] Resin Ex. Ex. Ex.Ex. Ex. Ex. Com. Com. Com. composition 13 14 15 16 17 18 ex. 4 ex. 5 ex.6 A-1 100 — — — — — — — — A-2 — 100 — — — — — — — A-3 — — 100 — — — — —— A-4 — — — 100 — — — — — A-5 — — — — 100 — — — — A-6 — — — — — 100 — —— B-1 — — — — — — 100 — — B-2 — — — — — — — 100 — B-3 — — — — — — — —100 Phthalkyd 60 60 60 60 60 60 60 60 60 V904 Titanium 33.3 33.3 33.333.3 33.3 33.3 33.3 33.3 33. dioxide Xylene 40 40 40 40 40 40 40 40 40(Abbreviation) Ex.: Example, Com. ex.: Comparative example

TABLE 6 Test results of painted film (Performance test of paint) Ex. Ex.Ex. Ex. Ex. Ex. Com. Com. Com. 13 14 15 16 17 18 ex. 4 ex. 5 ex. 6Adherence ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Weather Brightness   0 hr 85 84 85 83 82 8684 86 83 resistance (%)  200 hr 84 84 83 82 81 83 77 75 74  500 hr 82 8181 80 80 82 66 64 60 1000 hr 80 79 80 79 78 77 55 53 50 Warm waterresistance  120 hr ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ∘ Δ Δ (40° C.)  240 hr ∘ ∘ ∘ ∘ ∘ ∘ x x xMoisture resistance  120 hr ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Δ Δ Δ 50° C.—98% RH  240 hr ∘ ∘∘ ∘ ∘ ∘ x x x Evaluation criteria in table: ⊚ Good, ∘ Almost good, ΔSlightly poor, x Poor (Abbreviation) Ex.: Example, Com. ex.: Comparativeexample

Testing Methods of Painted Film 2 (Performance Test of Paint)

Adherence

A hundred cross-cuts reaching the base were made on the painted surfaceat intervals of 1 mm and cellophane adhesive tape was adhered closely.Then, it was peeled off in the direction of 180° to examine the numberof remaining cross-Cuts.

Accelerated Weather Resistance

carbon arc type sunshine weathermeter was used. The brightness wasmeasured with Hunter.

Warm Water Resistance

A painted plate was soaked for 120 hours and 240 hours into warm waterof 40° C. to examine the state of painted film. Moreover, a scratch (xmark) reaching the base was carved on the painted surface and cellophaneadhesive tape was adhered closely thereon. Then, it was peeled off inthe direction of 180° to examine the adherence of painted film.

Moisture Resistance

A specimen was allowed to stand for 120 hours and 240 hours in anatmosphere of 50° C. and relative humidity of 98%, and the state andadherence of painted film were examined by the method similar to thatfor warm water resistance.

Examples 19 Through 24 and Comparative Examples 7 Through 93

Sampling was made according to the formulation recipes of ink shown inTable 7 and, after kneading for 3 hour in a sand grinder mill, viscositywas adjusted with toluene so as to give 25 to 30 seconds/20° C. throughZahn cup No. 3 to make red ink.

Next, this red ink was coated onto an untreated polypropylene film(hereinafter referred to as untreated PP) and a corona treatedpolypropylene film (hereinafter referred to as treated PP) with coatingrod No. 14, respectively. After dried for 24 hours in the room,Cellotape peeling test using cellophane adhesive tape and heat sealstrength test were performed. The test results are shown in Table 8.

TABLE 7 Formulation recipe of ink [parts by weight] Resin Ex. Ex. Ex.Ex. Ex. Ex. Com. Com. Com. composition 19 20 21 22 23 24 ex. 7 ex. 8 ex.9 A-1 150 — — — — — — — — A-2 — 150 — — — — — — — A-3 — — 150 — — — — —— A-4 — — — 150 — — — — — A-5 — — — — 150 — — — — A-6 — — — — — 150 — —— B-1 — — — — — — 150 — — B-2 — — — — — — — 150 — B-3 — — — — — — — —150 Nippolan 67 67 67 67 67 67 67 67 67 5138 *Carmine 10.5 10.5 10.510.5 10.5 10.5 10.5 10.5 10.5 6BN *Carmine 6BN: Azo type organicpigment, red (from Tokyo Ink Mfg. Co.) (Abbreviation) Ex.: Example, Com.ex.: Comparative example

TABLE 8 Test results of ink Ex. Ex. Ex. Ex. Ex. Ex. Com Com Com 19 20 2122 23 24 ex. 7 ex. 8 ex. 9 Cellotape Untreated Good Good Good Good GoodGood Poor Poor Poor peeling PP Treated Good Good Good Good Good GoodPoor Good Good PP Heat seal Untreated 158 160 157 155 153 161 76 85 92strength PP (g/cm) Treated 255 280 275 266 271 287 135 155 152 PP(Abbreviation) Ex.: Example, Com ex.: Comparative example

Testing Methods of Ink

Cellotape Peeling Test

Cellophane adhesive tape was stuck on the ink-coated surface to judgethe peeling state of ink on the coated surface when peeling off at astroke.

Heat Seal Strength Test

The ink-coated surfaces were superposed one another and pressed for 2seconds at 110° C. under pressure of 1 kg/cm² to heat seal. Afterallowed to stand for 24 hours in the room, test of 180° peeling strengthwas performed with Tensilon. Pulling speed (50 mm/min).

Examples 25 Through 31 and Comparative Examples 10 Through 12

Solutions of chlorinated polyolefins of (A-1) through (A-6) and (B-1)through (B-3) were coated onto untreated PP and treated PP with coatingrod No. 20, respectively. After dried for 24 hours in the room, heatseal strength test was performed. The results of adhesion test are shownin table 9. Besides, the method of heat seal strength test was followedthe method as described above.

TABLE 9 Results of adhesion test Ex. Ex. Ex. Ex. Ex. Ex. Com Com Com 2526 27 28 29 30 ex. 10 ex. 11 ex. 12 Heat seal Untreated 345 368 371 355382 379 163 172 168 strength PP (g/cm) Treated 430 462 450 482 473 457268 289 276 PP (Abbreviation) Ex.: Example, Com ex.: Comparative example

Utilizability in the Industry

From the results in table 4, as Examples 1 through 6, carboxylgroup-containing chlorinated polyolefins (II) with low-molecular weightregion removed are excellent in the gasohol resistance, warm waterresistance and moisture resistance. Moreover, as Examples 7 through 12,even mixtures of said carboxyl group-containing chlorinated polyolefins(II) with alkyd resin, acrylic resin, polyacrylic polyol,polyesterpolyol, polyetherpolyol, polyurethane resin, etc. exhibit noremarkable decrease in the gasohol resistance and are also excellent inthe moisture resistance and warm water resistance. While, as Comparativeexamples 1 through 3, carboxyl group-containing chlorinated polyolefinswith low-molecular weight region unremoved show such results that thegasohol resistance becomes remarkably poor and the warm water resistanceand moisture resistance are slightly poor. Based on these facts, it isseen that the inventive primer compositions are useful for thepolyolefinic resin moldings.

From the results in Table 6, as Examples 13 through 18, the white paintsmade by mixing carboxyl group-containing chlorinated polyolefins (II)with low-molecular weight region removed with “Phthalkyd V904” being analkyd resin show no significant deterioration after each testing ofaccelerated weather resistance, water resistance and moistureresistance. However, as Comparative examples 4 through 6, with the whitepaints made similarly by using carboxyl group-containing chlorinatedpolyolefins with low-molecular weight region unremoved, yellowing wasseen on the painted surface after testing of accelerated weatherresistance and decreased adherence was seen after each testing of warmwater resistance and moisture resistance. Based on these facts, it isseen that the inventive paint compositions are useful for thepolyolefinic resin moldings.

From the results in Table 8, as Examples 19 through 24, the red inksmade by mixing carboxyl group-containing chlorinated polyolefins (II)with low-molecular weight region removed with “Nippolan 5138” being anurethane resin are excellent in the Cellotape peeling and heat sealstrength, compared with the red inks made similarly by using carboxylgroup-containing chlorinated polyolefins with low-molecular weightregion unremoved, as Comparative examples 7 and 8. Based on these facts,it is seen that the inventive ink compositions are useful for thepolyolefinic resin films.

From the results in Table 9, as examples 25 through 30, the systemswherein untreated PPs or treated PPs were stuck one another by heatsealing using carboxyl group-containing chlorinated polyolefins (II)with low-molecular weight region removed as an adhesive are excellent inthe adhesion strength, compared with the systems using carboxylgroup-containing chlorinated polyolefins with low-molecular weightregion unremoved as an adhesive. Based on these facts, it is seen thatthe inventive adhesive compositions are useful for the polyolefinicresin films.

What is claimed is:
 1. A binder resin for polyolefinic resins comprisingcarboxyl group-containing chlorinated polyolefin (II), which is acarboxyl group-containing chlorinated polyolefin obtainable by graftcopolymerizing at least one kind of unsaturated carboxylic monomerselected from carboxylic acid and/or carboxylic anhydride onto apolyolefin (I) in amounts of 1 to 10 wt. % and then chlorinating tochlorine content of 10 to 30 wt. %, which contains not more than 2% wt.of a component with molecular weight of 2,000 or lower, being thelow-molecular weight region of said carboxyl group-containingchlorinated polyolefin, and which carboxyl group-containing chlorinatedpolyolefin (II) has a ratio (Mw/Mn) of weight average molecular weight(Mw) to number average molecular weight (Mn) of not more than
 4. 2. Thebinder resin for polyolefinic resins of claim 1, wherein the polyolefin(I) is a polypropylene with weight average molecular weight of 10,000 to150,000, a propylene-α-olefin copolymer with weight average molecularweight of 10,000 to 150,000 containing 70 to 97 mol % of propylenecomponent and the number of carbon atoms of α-olefin is 2 or 4 to 6, ora propylene-butene-ethylene terpolymer with weight average molecularweight of 10,000 to 150,000 containing 70 to 97 mol % of propylenecomponent, 2 to 25 mol % of butene component and 2 to 25 mol % ofethylene component.
 3. The binder resin for polyolefinic resinscomprising the carboxyl group-containing chlorinated polyolefin (II) ofclaim 2 mixed with a resin selected from the group consisting of alkydresin, acrylic resin, polyacrylic polyol, polyesterpolyol, polyetherresin, polyetherpolyol, and polyurethane resin in proportion at a ratioby weight of 3:7 to 9:1.
 4. The binder resin of claim 2, wherein saidpolypropylene is a crystalline polypropylene.
 5. A primer compositionfor polyolefinic resins comprising the binder resin of claim
 2. 6. Apaint composition for polyolefinic resins comprising the binder resin ofclaim
 2. 7. An ink composition for polyolefinic resins comprising thebinder resin of claim
 2. 8. An adhesive composition for polyolefinicresins comprising the binder resin of claim
 2. 9. The binder resin forpolyolefinic resins comprising the carboxyl group-containing chlorinatedpolyolefin (II) of claim 1 mixed with a resin selected from the groupconsisting of alkyd resin, acrylic resin, polyacrylic polyol,polyesterpolyol, polyether resin, polyetherpolyol and polyurethane resinin proportion at a ratio by weight of 3:7 to 9:1.
 10. A primercomposition for polyolefinic resins comprising the binder resin of claim9.
 11. A paint composition for polyolefinic resins comprising the binderresin of claim
 9. 12. An ink composition for polyolefinic resinscomprising the binder resin of claim
 9. 13. An adhesive composition forpolyolefinic resins comprising the binder resin of claim
 9. 14. A primercomposition for polyolefinic resins comprising the binder resin ofclaim
 1. 15. A paint composition for polyolefinic resins comprising thebinder resin of claim
 1. 16. An ink composition for polyolefinic resinscomprising the binder resin of claim
 1. 17. An adhesive composition forpolyolefinic resins comprising the binder resin of claim
 1. 18. A methodof producing binder resin for polyolefinic resins comprising carboxylgroup-containing chlorinated polyolefin (II), which is a carboxylgroup-containing chlorinated polyolefin, which contains not more than 2%wt. of a component with molecular weight of 2,000 or lower, being thelow-molecular weight region of said carboxyl group-containingchlorinated polyolefin, and which carboxyl group-containing chlorinatedpolyolefin (II) has a ratio (Mw/Mn) of weight average molecular weight(Mw) to number average molecular weight (Mn) of not more than 4,characterized in that the low-molecular weight region of carboxylgroup-containing chlorinated polyolefin obtainable by graftcopolymerizing at least one kind of unsaturated carboxylic monomerselected from carboxylic acid and/or carboxylic anhydride onto apolyolefin (I) in amounts of 1 to 10 wt. % is removed by solventextraction within a temperature range of 10° C. to 100° C., using a solesolvent selected from a group consisting of aliphatic hydrocarbon,aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon,alcohols, esters, ketones and ethers with boiling point of lower than120° C. or a mixed solvent thereof, and then chlorination is conductedto a chlorine content of 10 to 30 wt. %.
 19. A method of producingbinder resin for polyolefinic resins comprising carboxylgroup-containing chlorinated polyolefin (II), which is a carboxylgroup-containing chlorinated polyolefin, which contains not more than 2%wt. of a component with molecular weight of 2,000 or lower, being thelow-molecular weight region of said carboxyl group-containingchlorinated polyolefin, and which carboxyl group-containing chlorinatedpolyolefin (II) has a ratio (Mw/Mn) of weight average molecular weight(Mw) to number average molecular weight (Mn) of not more than 4,characterized in that at least one kind of unsaturated carboxylicmonomer selected from carboxylic acid and/or carboxylic anhydride isgraft copolymerized onto a polyolefin (I) in amounts of 1 to 10 wt. %,and then the low-molecular weight region of carboxyl group-containingchlorinated polyolefin chlorinated to chlorine content of 10 to 30 wt. %is removed by solvent extraction within a temperature range of 0° C. to100° C., using a sole solvent selected from a group consisting ofaliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon,halogenated hydrocarbon, alcohols, esters, ketones and ethers withboiling point of lower than 120° C. or a mixed solvent thereof.